Soilproofing textiles with fiber-reactive fluoroalkyl derivatives of amino-aldehyde compounds



United States Patent F SOHPRGOFING TEXTILES WITH FIBER-REACTIVE FLUOROALKYL DERIVATIVES 0F AMINO-AL- DEHYDE CGMPOUND Domenick Donald Gagliardi, East Greenwich, R.I., as-

signor to Colgate-Palmolive Company, New York, N.Y., a corporation of Delaware No Drawing. Original application Sept. 30, 1963, Ser. No. 312,291, new Patent No. 3,296,264, dated Jan. 3, 1967. Divided and this application Oct. 4, 1966, Ser. No.

12 Claims. (U. 8-1163) This application is a division of application Ser. No. 312,291, filed Sept. 30, 1963, now Patent No. 3,296,264.

The present invention relates to textiles soilproofed by treatment with fiber-reactive fiuoroalkyl derivatives and more particularly textiles soilproofed with fiberreactive fiuoroalkyl derivatives of cyclic ureas, triazines and guanamines and to methods for producing such soilproofed textiles.

The treatment of textiles including fibers, yarns, woven fabrics, felted fabrics, and the like has been practiced for many centuries. At first man was concerned with imparting to textiles the capability of resistance to wetting by water. Many empirically developed mixtures have been applied to cloths to provide the Water-repelling rainwear which has in the past been known as macintoshe's. Everybody is acquainted with the coated fabric generally available as oil cloth. These early coated fabrics presented one surface which was a continuous film of the coating material which filled the interstices of the cloth, changed the porosity of the cloth, and the air permeability of the cloth. It was not until about 1935 that there was any attempt to discover the factors controlling resistance to wetting by water. Prior to this time, textile materials were coated with various cookbook recipes such as rubber, linseed oil-rubber mixtures, empirical and esoteric synthetic dopes and other compositions having no basis in a discovery of the physical properties of a preparation which would impart to a textile the capability of resisting wetting by Water or more briefly water repellency.

Without understanding the basic principles of the mechanism of conferring water repellency to textiles such as surface free energy, contact angle, and spreading coeflicient several unrelated practical developments arose during the period from 1935 to 1940 which changed the art of waterproofing textiles. In Germany, a series of parafiin wax emulsions were developed which, when padded onto textiles, produced a high contact angle of water drops on the surface and a high degree of shower resistancee without changing the porosity or air permeability of the textile material as do the preparations recommended for waterproofing prior to 1935. The fabrics treated with these parafiin-wax emulsions were not wettable by water and water-borne liquids and stains because of the change of the free energy of the fiber surfaces and not because the interstices of the woven fabrics were plugged. Thus, a practical improvement was made without an understanding of the reason for the advance in the art.

By the use of these new wax emulsion-metallic salts mixtures, it was then and is now possible to produce fabrics which have the feel and appearance of conventional fabrics but do not look like oil-cloths or fabrics having rubberized coating. The only partical limitation of such mixtures is the durability to washing and drycleaning. This class of waterproofing materials generally comprises a mixture containing:

(a) A paraffin wax or mixtures of vegetable wax esters such as Carnauba, Candilla, or sugar cane wax.

3,362,782 Patented Jan. 9, 1968 (b) An emulsifying agent, usually glue, gelatin and rosin soaps.

(c) An aluminum or zirconium salt, usually the formate or acetate. The primary function of the salt is to insolubilize the glue and other emulsifiers after the emulsion is deposited on the fabric.

A large variety of such products are still in use as lowcost, non-durable water repellents for textiles. Since neither thermosetting nor fiber reaction occurs when textiles are coated with such products, the treated textile is non-durable to washing and dry cleaning. Other than water repellency for rainwear fabrics, such mixtures provide fabrics with a fair degree of spot and stain resistance to water-borne chromophoric materials.

The search for durable or permanent Water repellents as contrasted with these non-durable water repellents, especially for cellulosic fibers was initiated by the need to overcome the deficiencies of these wax emulsionmetallic salt mixtures. The first major advance occurred in England where a product marketed under the trade name Velan with produced. This material was octadecyloxymethyl pyridiniurn chloride, a quaternary ammonium compound made by the chloromethylation of octadecanol, followed by quaternization with pyridine to yield a product having a composition represented by the formula H H C gHa7O omllro on O=C --C1- H H This compound, unlike other quaternaries, is unstable and under acid conditions reacts with surfaces containing active hydrogen, e.g., the hydrogen of a hydroxyl group in cellulose fibers. If the cellulose molecules be represented by Z(OH) then the reaction can be considered to be summarized by the equation:

where py is the balance of the pyridine ring. Fabrics treated with such a compound are durably water repellent, are porous, soft, and have the appearance of untreated fabrics.

A major improvement of the Velan type material was made when the stearamidomethyl analog of Velan Ci1H 5C ONHCHzN commercially known as Zelan and Norane R was produced. The advantage of the stearamide product is greater initial water repellency and greater durability to washing. Such products are still among the forefront of the leaders in rainwear fabric finishes.

In the search for other fabric-reactive or durable water repellents other classes of compounds have been developed. Illustrative of these other classes of water repellents are the silicone Water repellents methylolstearamide compositions (permel, Ahcovel NW), hydrophobic resins (Norane GG, Ranedare R, Argus DWR, octadecylketene dimer [Aquapel]) and others.

While durable water repellents had been initially developed for outerwear and raincoat applications, it was soon recognized that durable Water repellents could be used as finishes for other purposes. In the period 1950 to 1956 these durable water repellent finishes were widely used on mens suitings, dress goods, and upholstery materials. When offering these products to the textile finishing rade, promotional emphasis was not placed on waterepellency but on spot-and-stain resistance. This use has ontinued to the present time. It had been observed that abrics treated with such durable water repellents had a tigh degree of resistance to soiling by water-borne soils tnd stains and were easier to launder. The primary limiation of these finishes was that they attracted rather than 'epelled oily soils, and the treated fabrics were not re- :istant to staining by oily materials such as oils, greases, gravy, mayonnaise, etc.

In the early part of the 1950 decade based on work lone at Naval Research Laboratory by Fox and Zisman 1nd from work done at a division of the Minnesota Mining and Manufacturing Co., the utility of certain fluorozarbon based chemicals as fibrous finishes was announced. Fox and Zisman had demonstrated physiochemical principle of low free energy surfaces and the relation of nonwetting with water or oils of surfaces treated with chemicals containing perfiuoroalkyl groups.

The practical developments of 3M culminated in the introduction of the first product for textile treating. This product is still known as FC149 and is a classical Werner complex of a carboxylic acid made by reacting 1 mol of the acid with 2 mols of basic chromic chloride. The compound is water soluble and cationic in nature. It exhibits strong adhesion to anionic substrates such as cellulose and fiberglass. It also complexes with proteinaceous fibers such as wool, silk, and leather to give both water and oil repellent surfaces. It is generally believed that perfluorodecanoic acid is the base for this product.

Subsequently, 3M made a product known at FC208 available as a finish. It is generally believed that this finishing material is a perfluorosulfonamide polymer having a composition corresponding to the formula:

where x is an integer in the range of 3 to 13, R is methyl, ethyl, propyl, butyl, amyl, hexyl, R" is an alkylene radical having 1 to 12 carbon atoms and R' is hydrogen,

methyl, or ethyl.

The advent of these perfiuoro finishes produced a great practical improvement in fabric finishes. Although of little merit for plain Water repellency for outerwear purposes, the two products, i.e., the Werner Complex and the perfluorosulfonamide, offer a solution to the problem of providing fabrics with water-and-oil repellency and practical resistance to staining. Because of its hydrolytic instability the Werner complex has been limited to wool, leather, and upholstery finishes. The sulfonamide has become a leader in finishes for cotton, rayon, and non-celluloslc synthetic fiber.

Although important for water-and oil repellency and resistance to staining by water-and-oil borne stains for wearing apparel, upholstery and the like, the capability of shedding oily particulate soil is of greater importance. That is to say, the finely divided environmental grime mixed with the oil exudations of the human skin, i.e., oily particulate soil, soil in the neckband and cuffs of a mans shirt, are far more often encountered than soiling with gravy or mayonnaise. Hence, while fabric finishes which repel water, oil, water-borne and oil-borne stains are of great importance, the capability of resisting staining by oily particulate soil is of greater importance for aesthetic reasons if for no other reason. Yet even the perfiuoro finishes presently available do not have the capability of resisting staining by oily particulate soil. In fact they enhance such soiling.

It is manifest that controlled evaluating of fabric finishes in actual use is not possible. Consequently, it has been necessary to use evaluation methods subject to laboratory control which will simulate as closely as possible actual conditions under which water-repellency, oilrepellency, resistance to staining by water-borne and oilborne stains, and resistance to staining by oily particulate soil of treated fabrics occurs. Such methods of evaluation are the following.

WATER REPELLENCY Resistance to wetting (Spray Test) AATCC Standard Test Method 22-1952.This test is applicable to any textile fabric. It measures the resistance of fabrics to wetting by a water spray and the results depend primarily on the degree of hydrophobicity inherent in the fibers and yarns and subsequent treatments to which the fabric is subjected. Water is prayed against the taut surface of a test specimen. Evaluation of the wetted pattern is readily brought about by comparing the wetted pattern with standard wetting pattern pictures:

Rating: Characterized by 100 No sticking or wetting of the upper surface.

90 Slight random sticking or wetting of the upper surface.

Wetting of the upper surface at spray points.

70 Partial wetting of the whole of the upper surface.

50 Complete wetting of the whole of the upper surface.

0 Complete wetting of the whole of the upper and the lower surfaces.

The test specimens of minimum size of 7" x 7" (seven inches by seven inches) are conditioned at 70 F. and 65 percent relative humidity for a minimum of four hours before testing.

The test specimen, fastened securely and wrinkle-free in a metal hoop having a diameter of 6 inches, is placed and centered 6 inches under a standard spray nozzle at an angle of 45 to the horizontal. Two hundred and fifty milliliters of water at 80:2" F. is poured into a funnel attached above the spray nozzle. The spray lasts 25 to 30 seconds at the end of which time the hoop is taken by one edge and the opposite edge tapped smartly once against a solid object with the wet side facing the solid; this procedure is repeated with the hoop reversed 180.

OIL REPELLENCY 3M Textile Chemicals Appendix ATest Methods, page 1.The Minnesota Mining oil repellency test is based on the different penetrating properties of the two hydrocarbon liquids, mineral oil (Nujol) and n-heptane. (NujoP is the tradename for white mineral or parafiin oil being a mixture of hydro-carbons having a density for light oil in the range of 0.83 to 0.860 and for heavy oil in the range of 0.875 to 0.905.) The Nujol-heptane proportions for each rating were selected by 3M to give only stain resistance somewhat comparable to the water-borne stain resistance corresponding to each of the spray ratings of the AATCC Standard Test Method 22- 1952.

Oil Re-pellency Percent Heptane Percent- N njol Rating I (by volume) (by volume) 1 No hold out to Nujol.

The standard oil-heptane mixtures are contained in small stoppered medicine-dropper bottles. A drop of each mixture of NujoP and heptane is placed on the fabric.

The appearance of the test oil is observed through the drop. Note is made whether wetting or penetration occurs. The number corresponding to that mixture containing the highest percentage of heptane which does not penetrate or wet the fabric after three minutes is considered the oil repellency rating of the system.

The change in the optical refractivity of the drop is often an indication of wetting. In some cases wetting can be better determined by observing the other side of the fabric. In some cases reported hereinafter the term has been used to indicate a modicum of resistance to wetting by oil.

STAIN REPELLENCY The following procedures have been used to establish the degree of resistance to staining by water-borne and oil-borne stains of fabrics.

(a) The fabrics were stretched lightly on 12" x 31" frames. All or part of the frames Was used depending upon the amount of fabric available. The frames were supported at both ends with the fabric about 8 inches above a black surface. The fabric touched nothing.

(b) Three-inch medicine droppers were used to draw the stains from the containers. A 1 cubic centimeter calibration was established and marked on the exterior of each dropper. The stains were squeezed vertically downward from a height 2 inches above the cloth.

(c) After five minutes the unabsorbed stain was wiped ofi the fabric with two sweeps of Kleenex and the stains rated as follows.

Appearance: Rating No stain visible Slight stain 4 Easily noticeable stain 3 Considerable stain 2 Very heavily stained 1 (The spread or lack of spread is not necessarily reflected in the ratings.)

(d) Duplicate sets of stains were applied in separate areas so that one-half of the fabric could be washed. In most instances, the wash was carried out with 50 grams of FAB, a cotton cycle, and a dummy load to total 5 pounds in a Norge Home Automatic Washer.

(e) The following two lists describe the numbering and the gross characterizations of the stains employed.

Water Stains:

(1) Instant Tea a (2) Shealfers 232 Blue-black skrip (3) A & P Concord Grape Juice (4) Ann Page Salad Mustard (5 Bosco chocolate syrup Oil Stains:

(6) Wesson Oil (7) Gulf Supreme Motor Oil 20/20 (8) Oleomargarine (9) La Rosa Tomato Sauce (10) Jergens Lotion e 8 cc. dry powder/200 cc. water applied at 160 F.

b Melted and applied at 160 F.

In reporting the relative resistance to staining and ease of stain removal in laundering, the staining values for water-borne and oil-borne stains were averaged separately.

In all cases the stains were allowed to dry on the fabrics for twenty-four hours before laundering.

OILY PARTICULATE SOIL REPELLENCY (GRC Dry Soil Test).-Fifteen to twenty 6" x 8" numbered specimens (normally 80 x 80 cotton), including at least one untreated control, are tumbled for thirty minutes with 10 percent of Cyanamid Soil based on the weight of the fabric. The tumbling is carried out in a 5 liter capacity Five Minute Home Cleaner at 44 r.p.m.; six No. 8 Neoprene rubber stoppers are distributed among the specimens to increase the mechanical action. At the 6 end of tumbling, the specimens are removed and each shaken separately up and down fifteen times by hand to remove surface dirt.

The specimens are then cut in two (to produce two 4" x 6" pieces). One-half is washed with 50 grams of FAB in a cotton cycle with a S-pound dummy load, tlllen hung to dry and lightly ironed under a clean cotton 0 0th.

The degree of soiling is determined with a Photovolt Reflectance Meter (Tn' Blue Filter). Six readings per specimen are made and the arithmetic average reported.

The Cyanamid Soil described below is the same as that recommended by Minnesota Mining and Manufacturing Co. The following dry ingredients are blended thoroughly, dried in a forced draft convection oven for eight hours at 50 C., then milled for twenty-five hours with ceramic balls and stored in a polyethylene bag.

CYANAMID SOIL Material: Percent by weight Peat Moss 38 Cement 17 Kaoline Clay 1 l7 Silica, 200 mesh 2 17 Furnace Black 1.75 Red Iron oxide 4 0.50 Mineral Oil 8.75

1 Peerless R. T. Vanderbilt.

2 Davison Chemical Co.

3 Molacco Benny and Smith Co.

4 C. K. Williams 00.

It has now been discovered that textiles may be soilproofed by treatment with fiber-reactive fiuoroalkyl derivatlves of amino-aldehyde compounds, i.e., fiuoroalkyl denvatives of monocyclic ureas and thioimino compounds having compositions corresponding to the formula:

where Q is a fiuoroalkyl group having four to twelve (inclusive) carbons atoms in which at least 70 percent to percent of the (Tn+l) hydrogen atoms (n=4 to 12) has been replaced by fluorine atoms and at least two and preferably three fluorine atoms are attached to the terminal or omega carbon atom; X is or 0, R is hydrogen, CH C H C3H7; m is one to five dependent upon the functionality of the amido residue; n is at least one; (m+n) is two to six inclusive; R is a divalent radical selected from the group:

Monocyclic Ureas Y N/ \N where Y is 0:0, C=NH, C=S; and Z is CH CH CH CH OCH R has the significance given hereinbefore,

Diheterocyclic Ureas where Y and R have the significance given hereinbefore,

Trz'azines and Specific examples include: ethylene urea, propylene urea, uron, triazones, acetylene diurea, dimethylacetylene diurea, melamine, and acetoguanamine.

There can be one (QXCH group or as many as five, depending upon the functionality of the amido residue. There must always be at least one (-CH OR')- group remaining for reaction with the fiber, e.g., with cellulose (ZOH) or when more than two (CH OR')-groups are present for the formation of a thermosetting resin. Both of these reactions, i.e., with the active hydrogen of the fiber or the formation of a thermosetting resin, are catalyzed by acidic catalysts such as zinc nitrate, magnesium chloride, oxalic acid, ammonium chloride, and the like.

The fluoroalkyl group Q is derived from alcohols or amides. The fiuoroalkyl cyclic amido compounds are prepared either by ether interchange or by direct fiuoroalkylation. Thus, fluoroalkoxymethyl-penta (methoxymethyl) melamine where Q is --CH (CF CF has been prepared by reacting hexa (methoxymethyl) melamine and pentadecafluorooctyl alcohol in equimolar proportions using about 0.05 part by weight of 85 percent orthophosphoric acid as the ether interchange catalyst. The reaction mixture was heated from 103 C. to 153 C. in about thirty minutes during which time an amount of methanol was collected indicating the replacement of one methyl group by the pentadecafiuorooctyl group and the formation of the pentadecafluorooctoxymethylpenta (methoxymethyl) melamine. Pentadecafiuorooctoxymethylpenta (methoxymethyl) melamine and the other fiuoroalkyl derivatives of amino-aldehyde compounds within the scope of formula (B) supra are reactive with textile materials having active hydrogen atoms in the surfaces thereof.

Equirnolar amounts of C trihydroperfluoroalkyl alcohol (CI-IF (CF CH OH) and tetramethylolacetylene monourine were condensed using 85 percent phosphoric acid as the condensation catalyst. An amount of water was stripped indicating the formation of the C trihydroperfluoroalkyl trimethylolacetylene monourein.

The general procedure for treating textile materials involves padding the textile to at least 80 percent wet pickup with 0.1% to solution of the fluoro compound and curing the so-treated textile from room temperature 8 to 350 F. An acid catalyst may be used in the padding bath.

EXAMPLE 1 The C trihydroperfluoroalkyl, trimethylolacetylene monourein was padded on x 80 cotton from 3 percent isopropanol solution (Run No. 1) and from 3 percent isopropanol solution in the presence of a zinc complex as a catalyst (Run No. 2). The degree of soil proofing conferred on the textile is indicated by the values reported in the following table.

Cured at Room, Temperature Percent Run No. Catalyst Reflectance Repellencies, Oil

Untreated Cotton 0 2G 77 1 0 S0 43 81 2 1. 5 8O 36 81 EXAMPLE 2 A textile material is padded to 80% wet pick-up with a solution of pentadecafluorooctoxymethylpenta (methoxymethyl) melamine and cured at room temperature.

EXAMPLE 3 Example 2 is repeated using C trihydroperfiuoroalkyltrimethylolacetylene diureine.

The heterocyclic nitrogen bases of the present invention are not to be confused with what seems to be similar compositions previously known to the art. For example in US. Patent No. 2,421,707 there are disclosed a group of Wetting, detersive, and dispersing agents which may be represented by the general formula:

A soil proofing textile finishing agent is not suggested by nor the same as, wetting detersive and dispersing agents.

In US. Patent No. 2,508,652 similar piperazine and alkyl substituted piperazines conforming to the general formula where X is R or RG0; A and B are unsubstituted ethylene radicals or ethylene radicals having one to four short chain alkyl substituents of not more than two carbon atoms; R is a lon -chain aliphatic radical such that the carbon content of X is from, six to twenty-four carbon atoms; R is a short-chain alkyl of acyl radical; and n is 1 to 9, are described. These piperazines are said to be suitable for softening fabrics, fixing colors, removing grease and oil, and penetrating and in ore flotation as addition agents. In other words, these piperazines are of the nature of surfactive agents with no suggestion that such materials when applied to textiles will shed oily particulate soil.

Novel detergents conforming to the general formula:

where R is an alkyl or acyl radical having five to twentythree carbon atoms; A and B are ethylene radicals wherein any number of hydrogen atoms (none, one or more) are replaced by alkyl radicals; and m and n are integers in the range of two to five are disclosed in US. Patent No. 2,634,239. It is trite to remark that detergents are not suggestive of soil-proofing finishing agents.

I claim:

1. A method of soilproofing textile material which comprises treating said textile with from 0.1% to 10% of a heterocyclic nitrogen base having the composition corresponding to the formula where Q is a fluoroalkyl group having four to twelve (inclusive) carbon atoms in which at least 70 percent to 100 percent of the (2n+1) hydrogen atoms (n=4 to 12) has been replaced by fluorine atoms and at least two and preferably three fluorine atoms are attached to the terminal or omega carbon atom; X is l dNH- or O-, R is hydrogen, CH C H C3H7, m is one to five dependent upon the functionality of the amido residue; n is at least 1; (m+n) is two to six inclusive, R is a divalent radical selected from the group consisting of Monocyclic Ureas z where Y is (3:0, C=NH, C=S, and Z is CH CH CH -CH OCH R' has the significance given hereinbefore,

Diheterocyclic U reas II.

where Y and R have the significance given hereinbefore Triazines III and

Guanamines IV N and curing the treated textile.

2. A method as defined in claim 1 wherein the textile is padded to at least 80% wet pick-up with a solution of said heterocyclic nitrogen base.

3. A method as defined in claim 1 wherein the heterocyclic nitrogen base is pentadecafluorooctoxymethylpenta (methoxyrnethyl) melamine.

4. A method as defined in claim 1 wherein the heterocyclic nitrogen base is C trihydroperfluoroalkyltrimethylolacetylene diureine.

5. A method as defined in claim 1 wherein the textile is cured at a temperature from room temperature to 6. A method as defined in claim 1 wherein an acid catalyst is employed in the treatment.

7. A method as defined in claim 5 wherein an acid 15 catalyst is employed in the treatment.

8. A method as defined in claim 2 wherein an acid catalyst is present in the padded solution.

9. A method as defined in claim 8 wherein the textile material is cured at a temperature from room temperature to 350 F.

10. Textile material produced in accordance with the method of claim 1.

11. Cellulosi-c textile material having chemically reacted therewith so as to provide a soilproofed finish on heterocyclic nitrogen base of the formula where Q is a fluoroalkyl group having four to twelve (inclusive) carbon atoms in which at least 70 percent to 0 100 percent of the (2n+1) hydrogen atoms (n=4 to 12) has been replaced by fluorine atoms and at least two and preferably three fluorine atoms are attached to the terminal or omega carbon atom; X is i)-NH or -O, R is hydrogen, CH C H C H m is one to five dependent upon the functionality of the amido residue; n is at least 1; (m+n) is two to six inelusive, R is a divalent radical selected from the group consisting of Monocyclic Ureas r. Y

where Y is C=O, C=NH, C=S, and Z is CH CH -CH CH CH CH OCH CHzlYI-OH2 R has the significance given hereinbefore,

Diheterocyclic Ureas II. /Y

G OR I I where Y and R have the significance given hereinbefore and Guanamines 12. Cellulosic textile material as defined in claim 11 wherein R is a diheterocyclic urea.

NORMAN G. TORCHIN, Primary Examiner.

J. CANNON, Assistant Examiner. 

1. A METHOD OF SOILPROOFING TEXTILE MATERIAL WHICH COMPRISES TREATING SAID TEXTILE WITH FROM 0.1% TO 10% OF A HETEROCYCLIC NITROGEN BASE HAVING THE COMPOSITION CORRESPONDING TO THE FORMULA 